Bridged ketones, process for preparing same and use thereof in augmenting or enhancing fabric softeners

ABSTRACT

Described is a process for augmenting or enhancing the aroma of a dryer-added fabric softener article comprising the step of intimately admixing with the coating composition for the outer coating of said dryer-added fabric softener article an aroma augmenting or enhancing quantity of at least one tricyclic ketone having the structure: ##STR1## wherein R 1 , R 2  and R 3  are the same or different and each represents hydrogen or C 1  -C 3  lower alkyl.

This application is a divisional of application for U.S. Letters Patent,Ser. No. 095,149 filed on Nov. 16, 1979, now U.S. Pat. No. 4,250,338issued on Feb. 10, 1981.

BACKGROUND OF THE INVENTION

This invention relates to compounds having the generic structure:##STR2## wherein R₁, R₂ and R₃ are the same or different and eachrepresents hydrogen or C1-C3 lower alkyl, processes for preparing sameand organoleptic uses thereof in perfumes, colognes, perfumed articlessuch as anionic, cationic and nonionic detergents and dryer-added fabricsofteners and in smoking tobaccos and smoking tobacco articles whichcomprise a wrapper encasing a smoking tobacco body and impingingthereupon a smoking tobacco article filter.

There has been considerable work performed relating to substances whichcan be used to impart (modify, augment or enhance) flavors andfragrances to (or in) various consumable materials. These substances areused to diminish the use of natural materials, some of which may be inshort supply, and to provide more uniform properties in the finishedproduct.

Low-keyed, oily, woody, amber, leathery, warm spice, earthy,camphoraceous, patchouli-like, balsamic, green, cardamom-like,vetiver-like, sweet woody, amber and minty aromas are desirable inseveral types of perfume compositions, perfumed articles such asanionic, cationic and non-ionic detergents, cosmetic powders anddryer-added fabric softener articles, and colognes.

Sweet, floral, woody, spicy, leathery and amber aromas prior to smokingand sweet, natural tobacco-like tastes and aromas are desirable inseveral types of smoking tobaccos, smoking tobacco articles and insmoking tobacco flavoring compositions.

British Pat. No. 896,039 entitled "Method of Producing Derivatives ofthe 1,1-Dimethyloctahydronaphthalene Series" discloses the genericprocess ##STR3## wherein R₂, R₃, and R₄ are disclosed to be same ordifferent hydrogen atoms or alkyl and R₁ is disclosed to be hydroxy,alkyl or alkoxy. The British patent discloses this process to be usefulfor producing products "resembling the well known class of violetperfumes". Indeed, Example 5 of the British patent alleges that thecompound 1,1,6,6-Tetramethyl-7-ketomethyl-Octalin produced by (1)reacting myrcene and mesityl oxide thermally followed by (2) subsequentcyclization, has a pleasant "woody ambergris smell". However, arepetition of the teachings of this British patent gives rise to thefollowing results:

STRUCTURE OF COMPOUND ##STR4## NAME1',2',3',4',5',6',7',8'-octahydro-8',8'(and5',5')dimethyl-2'-naphthaldehyde PERFUME PROPERTIES

Green, fruity

STRUCTURE OF COMPOUNND ##STR5## NAME1',2',3',4',5',6',7',8'-octahydro-2',8',8'(and2',5',5')-trimethyl-2',napthaldehyde Perfume Properties

Green floral, fruity

STRUCTURE OF COMPOUND ##STR6## NAME1',2',3',4',5',6',7',8'-octahydro-3',8',8'(and3',5',5')-trimethyl-2'-naphthaldehyde Perfume Properties

Green, buttery, woody

U.S. Pat. No. 2,933,506, issued on Apr. 19, 1960, discloses theproduction of perfume compounds according to the reaction sequence:##STR7##

In said formula R₁, R₂, R₃, and R₄ represent hydrogen or alkyl,especially a lower alkyl radical, aryl, aralkyl, cycloalkyl, orheterocyclic residues. R₁ in said formula can also be the hydroxyl groupor an ether group. The ether group may form an ester group or a lactonegroup with the --CO-- group.

The new compounds are obtained by first subjecting myrcene of Formula Ito the diene synthesis with a dienophilic compound of Formula II. Theresulting adduct of Formula III is then subjected to ring closurereaction to form the corresponding 1,1-dimethyl octaline compounds ofFormula IV.

Thus, for example, the 1,1-dimethyl-7-methylal octaline can be producedas follows:

576 g. (3 mols) of the aldehyde obtained from myrecene and acrolein,said aldehyde corresponding to Formula III wherein R₁, R₂, R₃, and R₄are hydrogen, are dissolved in 600 cc. of ether. 279 g. (3 mols) ofaniline dissolved in 500 cc. of ether are added to said solution portionby portion at room temperature in a separatory funnel while shaking themixture repeatedly.

After allowing the mixture to stand at room temperature for about 20hours, the theoretical amount of water has split off. The resultingsolution is separated from the water formed on reaction and is directlyused for cyclization.

The ethereal solution of the Schiff's base is added drop by drop to 4 l.of 62% sulfuric acid at -15° C. within about 2 hours while stirringvigorously. Care must be taken that the temperature does notsubstantially exceed 0° C. After the solution has been added to thesulfuric acid, stirring of the reaction mixture is continued at -5° C.for about one hour. The reaction mixture is then treated with steamuntil all the solvent has been distilled off. The distillation requiresabout 1/2 hour. The reaction mixture has now separated into two layers.It is poured on ice and is exhaustively extracted with benzene. Thebenzene solution of the bicyclic aldehyde is washed with water until thewash water is substantially neutral. Thereafter, the solvent isdistilled off under atmospheric pressure and the residue is subjected tofractional distillation in a vacuum.

In this manner 438 g. of 1,1-dimethyl-7-methylal octaline are obtained.The yield is about 76% of the theoretical yield. The reaction productconsists to 2/3 of the β-compound with the double bond in 9,10-positionand to 1/3 of a substantially uniform isomer, the double bond of whichis either in α-, or in γ-, or in δ-position.

Characteristic properties of the mixture of isomers:

Boiling point: 85°-86° C./0.5 mm.:

Denisty d₄ ²⁰ : 0.9877;

Index of refraction n_(D) ²⁰ : 1.5031;

Aldehyde content: 98-100%.

By fractional crystallization of the semicarbazones of the reactionmixture, the isomers can be separated from each other. For this purpose70 g. of the bicyclic aldehyde mixture are mixed with a solution of 70g. of semicarbazide hydrochloride and 70 g. of sodium acetate in 140 cc.of water. Methanol is added until complete solution is achieved. Thereaction mixture is allowed to stand overnight at room temperature. 95.5g. of an amorphous semicarbazone precipitates. It has an unsharp pointof decomposition at 139°-141° C. On repeated recrystallization from 90%methanol, 53.5 g. of white crystals melting at 148° C. withdecomposition are obtained.

In order to produce therefrom pure 1,1-dimethyl-7-methylal-Δ₉,10-octaline, the semicarbazone was split up by heating with 50 g. ofoxalic acid in 200 cc. of water. The aldehyde set free thereby isseparated from the reaction solution by vacuum steam distillation. Thesteam distillate is subjected to fractional distillation in a vacuum. Inthis manner 30 g. of a very pure aldehyde are obtained. This aldehydehas a pleasant refreshing and sandalwood-like ionone odor.

Characteristic properties of 1,1-dimethyl-7-methylal-Δ₉,10 -octaline:

Boiling point: 85° C./0.5 mm.;

Density d₄ ²⁰ : 0.9914;

Index of refraction n_(D) ²⁰ : 1.5054;

Aldehyde content: 100%.

After standing for several days at -25° C. there precipitates from themother liquor of the semicarbazone reaction mixture a second compoundwhich, on repeated recrystallization from methanol, has a melting pointof 134° C. 14.5 g. of this semicarbazone are obtained. The aldehyde isset free therefrom by means of oxalic acid in the same manner asdescribed hereinabove for the β-aldehyde.

The position of the double bond in said aldehyde could not yet beascertained with certainty. The double bond is either in α-, γ-, orδ-position. The compound also has a refreshing ionone aroma, however,without any accompanying sandalwood-like nuance.

Characteristic properties of this isomeric aldehyde:

Boiling point: 85°-86° C./0.5 mm.,

Density d₄ ²⁰ : 0.9890;

Index of refraction n_(D) ²⁰ : 1.5044;

Aldehyde content: 100%.

Another example indicating preparation of 1,1-dimethyl-7-methylaloctaline in U.S. Pat. No. 2,933,506 is as follows:

1 mol. of the aldehyde in the form of its Schiff's base as prepared andused in Example 1 is dissolved in an equal amount of benzene. Thebenzene solution is added drop by drop to 700 cc. of 85% phosphoric acidat 0° C. while stirring vigorously. Thereafter, stirring of the reactionmixture is continued at 60° C. for 1 hour. Thereby not only cyclizationis completed but the azomethine group is quantitatively split up. Theresulting bicyclic aldehyde is then poured on ice, extracted by means ofbenzene, and the benzene layer is washed with water until neutral. Afterdistilling off the solvent, 190 g. of residue of an aldehyde content of82% are obtained. The crude bicyclic aldehyde is subjected to fractionaldistillation by means of a small fractionating column. In this manner135 g. of 1,1-dimethyl-7-methylal octaline are obtained. The yield isabout 70% of the theoretical yield. The aldehyde consists mainly of anisomer, the double bond of which is either an α-, or in γ-, or inδ-position.

Characteristic properties:

Boiling point: 96° C./0.7 mm.;

Density d₄ ²⁰ : 0.9884;

Index of refraction n_(D) ²⁰ : 1.5042;

Aldehyde content: 98-100%.

Additional reaction of the resulting compounds with acid and heatinggives rise to the compounds of our invention having the genericstructure: ##STR8## wherein R₁, R₂ and R₃ are the same or different andeach represents hydrogen or C1-C3 lower alkyl.

However, there is no inference in any of the pertinent prior art thatthe tricyclic ketone compounds of our invention can by produced or everhave been produced.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 represents the NMR spectrum for the tricyclic ketone compoundhaving the structure: ##STR9## produced according to Example I.

FIG. 2 represents the infra-red spectrum for the tricyclic ketonecompound having the structure: ##STR10## prepared according to ExampleI.

FIG. 3 represents the GLC profile for the reaction product of ExampleIII.

FIG. 4 represents the NMR spectrum for the aldehyde produced accordingto Example IV, having the structure: ##STR11##

FIG. 5 represents the infra-red spectrum for the aldehyde having thestructure: ##STR12## produced according to Example IV.

FIG. 6 represents the NMR spectrum for the mixture of aldehydes producedaccording to Example V, having the generic structure: ##STR13##

FIG. 7 represents the infra-red spectrum for the mixture of aldehydesproduced according to Example V, having the generic structure: ##STR14##wherein one of the dashed lines represents a carbon-carbon double bondand the other of the dashed lines represents carbon-carbon single bonds.

FIG. 8 represents the GLC profile for the product produced according toExample V, containing the aldehydes having the generic structure:##STR15##

FIG. 9 represents the NMR spectrum for the tricyclic ketone havine thestructure: ##STR16## produced according to Example VI.

FIG. 10 represents the infra-red spectrum for the tricyclic ketonehaving the structure: ##STR17## produced according to Example VI.

FIG. 11 represents the NMR spectrum for the tricyclic ketone producedaccording to Example VII, having the structure: ##STR18##

FIG. 12 represents the ¹³ C NMR spectrum for the tricyclic ketone havingthe structure: ##STR19## produced according to Example VII.

FIG. 13 represents the NMR spectrum for the tricyclic ketone having thestructure: ##STR20## produced according to Example VIII.

FIG. 14 represents the infra-red spectrum for the tricyclic ketonehaving the structure: ##STR21## produced according to Example VIII.

THE INVENTION

It has now been discovered that novel smoking tobacco and smokingtobacco flavoring compositions having sweet, floral, woody, spicy,leathery and/or amber aroma and taste nuances prior to smoking and sweetnatural tobacco tastes and aromas on smoking both in the main stream andthe side stream, as well as novel perfume compositions, colognes andperfumed articles (e.g., solid or liquid anionic, cationic and non-ionicdetergent compositions, as well as dryer-added fabric softener articles,as well as cosmetic powders) having intense and pleasant oily, woodyamber, leathery, warm spice, earthy camphoraceous, patchouli-like,balsamic, green, cardamom-like, vetiver-like, sweet woody, amber andminty aromas may be provided by the utilization of one or more tricyclicketone derivatives having the generic structure: ##STR22## wherein eachof R₁, R₂ and R₃ are the same or different and each represents hydrogenor C1-C3 lower alkyl, such as methyl, ethyl, n-propyl and i-propyl.

The novel tricyclic ketones of our invention useful as indicated supra,may be produced preferably by one of the following processes:

(1) First reacting myrcene having the structure: ##STR23## with analpha, beta unsaturated aldehyde having the generic structure: ##STR24##wherein R₁, R₂ and R₃ are the same or different hydrogen or lower alkylin the presence of a Lewis acid catalyst such as aluminum trichloride,boron trifluoride, stannic fluoride, zinc fluoride zinc bromide, ethylaluminum dichloride or diethyl aluminum monochloride or, in the absenceof catalysts under conditions of higher temperatures, 50°-150° C., toproduce an unsaturated aldehyde or a mixture of unsaturated aldehydeshaving the generic structure: ##STR25## Depending upon the catalystused, the proportion of one isomer to the other isomer of resultingaldehyde will vary.

The aldehydes having the generic structures: ##STR26## are eitherseparated by standard means of physical separation, e.g., fractionaldistillation or industrial column chromatography, or they are permittedto remain as a mixture. These aldehydes are then reacted in the presenceof acid, such as phosphoric acid or sulfuric acid, in order to producecyclic aldehydes having the generic structure: ##STR27## wherein one ofthe dashed lines represents a carbon-carbon double bond and each of theother dashed lines represents carbon-carbon single bonds, and whereinR₁, R₂ and R₃ are the same or different hydrogen or C1-C3 lower alkyl.

When the aldehyde having the structure: ##STR28## is reacted alone, theresulting aldehyde has the generic structure: ##STR29## and is, ofcourse, a mixture of aldehydes. Insofar as our invention is concerned,the only useful aldehyde to be reacted for producing compounds havingthe generic structure: ##STR30## is the aldehyde having the structure:##STR31## This aldehyde will form the mixture of aldehydes having thestructure: ##STR32## which in turn is reacted under acid conditions,(either Lewis acid or mineral acid) to form the tricyclic ketone havingthe structure: ##STR33## according to the mechanism: ##STR34##

In the alternative, the aldehyde having the structure: ##STR35## mayfirst be reacted with an amine R'NH₂ to form an imine having the genericstructure: ##STR36## which in turn is cyclized in the presence ofmineral acid or Lewis acid to form the mixtures of compounds having thestructures: ##STR37## wherein R' is lower alkyl and R₁, R₂ and R₃ arethe same or different hydrogen or lower alkyl and one of the dashedlines is a carbon-carbon double bond and each of the other dashed linesrepresents carbon-carbon single bonds.

The resulting mixture of aldehydes having the structure: ##STR38## butnot the mixture of aldehydes having the structure: ##STR39## or theresulting imine having the structure: ##STR40## is thus reacted to formthe novel compounds of our invention having the structure: ##STR41## inthe presence of acid.

The condition for the Diels-Alder reaction between myrcene, having thestructure: ##STR42## and the alpha, beta unsaturated aldehyde, havingthe structure: ##STR43## as well as the conditions for the reaction ofthe compounds having the structures: ##STR44## to form the cycliccompounds having the structures: ##STR45## are set forth in theliterature as follows: 1. U.S. Pat. No. 3,911,018 issued on Oct. 7,1975, at Columns 7, 8 and 9 thereof.

2. U.S. Pat. No. 2,933,506 issued on Apr. 19, 1960, at Examples 1, 2 and3 at Columns 6, 7 and 8 thereof.

In the reaction to form the tricyclic ketone having the structure:##STR46## from the aldehyde having the structure: ##STR47## the mineralacids which can be used are hydrochloric acid, sulfuric acid, phosphoricacid, or paratoluene sulfonic acid. An inert solvent is used in thisreaction, xylene, toluene, benzene or diethylbenzene, or a chlorocarbonsuch as chloroform (CHCl₃) or methylene chloride (CH₂ Cl₂).

The mole ratio of aldehyde having the structure: ##STR48## may vary from1:10 up to 10:1 with a range of mole ratios of from about 1:2 up toabout 1:0.5 being preferred.

The temperature of reaction may vary from 25° C. up to 100° C. with atemperature range from about 60° C. up to about 80° C. being preferred.

In place of the mineral acid being used, a Lewis acid may be used, suchas aluminum chloride, stannic chloride, titanium tetrachloride, borontrifluoride, or boron trifluoride etherate, ethyl aluminum chloride,ethyl aluminum dichloride, zinc bromide or zinc chloride. Thetemperature of reaction may vary from 25° C. up to 100° C. with atemperature of from 25° C. to 45° C. being preferred. The mole ratio ofaldehyde having the structure: ##STR49## may vary from 1:1 up to 1:2with an inert solvent being used which is either toluene, benzene,xylene, diethylbenzene, chloroform or methylene chloride.

The time of reaction for forming of the compounds represented by thegeneric structure: ##STR50## using the compounds represented by thegeneric structure: ##STR51## may vary from about 1 hour up to about 12hours when operating at reflux temperatures, such as 110°-120° C., usinga toluene solvent. Preferred is a reaction time of between 5 and 12hours.

It is noteworthy that whereas the genus of compounds having thestructure: ##STR52## will react to form the genus of compounds havingthe structure: ##STR53## the genus of compounds having the structure:##STR54## will not so react when treated with either Lewis acid ormineral acid under high temperature conditions. This gives rise to theadvantage of separating out the isomeric components of compounds havingthe structures: ##STR55## or compounds having the structures: ##STR56##

Examples of the tricyclic ketone compounds having the generic structure:##STR57## produced according to the processes of our invention and theirorganoleptic properties are set forth in the following table:

                                      TABLE I                                     __________________________________________________________________________                                              SMOKING TOBACCO                     STRUCTURE  NAME OF COMPOUND                                                                             PERFUMERY EVALUATION                                                                          FLAVOR EVALUATION                   __________________________________________________________________________     ##STR58## hexahydro-5,5-dimethyl-2H- 2,4-a-methanonaphthalene- 1(5H)-one                               A sweet, woody, camphor- aceous aroma with                                    minty and ambery nuances.                            ##STR59## hexahydro-2,5,5-trimethyl- 2H-2,4-a-methanonaphthalene-                       1(5H)-one      A low-keyed, oily, woody, amber aroma with                                    woody and slightly leathery undertones. On                                    purifica- tion a deep woody, earthy camphoraceou                              s, patchouli- like aroma with amber and                                       leathery undertones.                                                                          Prior to smoking a sweet,                                                     floral, musty, woody, spicy and                                               leathery and amber-like aroma                                                 and taste. On smok- ing, a                                                    sweet, floral, musty, woody,                                                  spicy, leathery, amber-like                                                   aroma with a slight cooling                                                   effect in both the main stream                                                and the side stream. When added                                               to a fil- ter, a sweet aroma                                                  with enhanced tobacco taste and                                               aroma of very natural quality                                                 is obtained in the main stream                                                and the side stream.                 ##STR60## hexahydro-1,5,5-trimethyl- 2H-2,4-a-methanonaphthalene-                       1(5H)-one      A woody aroma with green, tart, cardamom-like                                 un- dertones.                                        ##STR61## hexahydro-1,2,5,5-tetramethyl- 2H-2,4-a-methanonaphthalene-                   1(5H)-one      A sweet woody, camphoraceous, balsamic aroma                                  with patchouli and deep woody                                                                 A floral ionone- like aroma                                                   with woody, balsamic nuances                                                  prior to and on smoking both in                                               the main stream and the side                                                  stream.                             __________________________________________________________________________

One or more of the tricyclic ketones of our invention and one or moreauxiliary perfume ingredients including, e.g., alcohols, aldehydes,ketones other than the tricyclic ketones of our invention, terpenichydrocarbons, nitriles, esters, lactones, natural essential oils andsynthetic essential oils, may be admixed so that the combined odors ofthe individual components produce a pleasant and desired fragrance,particularly in the woody, ambery, leathery, patchouli-like and vetiverfragrances. Such perfume compositions usually contain (a) the main noteor the "bouquet" or foundation stone of the composition; (b) modifierswhich round off and accompany the main note; (c) fixatives which includeodorous substances which lead a particular note to the perfumethroughout all stages of evaporation and substances which retardevaporation; and (d) topnotes which are usually low boiling freshsmelling materials.

In perfume compositions, it is the individual components whichcontribute to their particular olfactory characteristics, however theover-all sensory effect of the perfume composition will be at least thesum total of the effects of each of the ingredients. Thus, one or moretricyclic ketone derivative(s) of our invention can be used to alter,modify or enhance the aroma characteristics of a perfume composition,for example, by utilizing or moderating the olfactory reactioncontributed by another ingredient in the composition.

The amount of tricyclic ketone derivative(s) of our invention which willbe effective in perfume compositions as well as in perfumed articles andcolognes depends on many factors, including the other ingredients, theiramounts and the effects which are desired. It has been found thatperfume compositions containing as little as 0.01% of tricyclic ketonederivative(s) or even less (e.g., 0.005%) can be used to impart avetiver aroma with sweet woody, citrusy, musky, woody/peppery,woody/leathery, hay and green nuances to soaps, cosmetics, detergents,powders and colognes. The amount employed can range up to 70% of thefragrance components and will depend on considerations of cost, natureof the end product, the effect desired on the finished product and theparticular fragrance sought.

The tricyclic ketone derivative(s) of our invention are useful [takenalong or together with other ingredients in perfume compositions] as(an) olfactory component(s) in detergents and soaps, space odorants anddeodorants, perfumes, colognes, toilet water, bath preparations, such aslacquers, brilliantines, pomades and shampoos; cosmetic preparations,such as creams, deodorants, hand lotions and sun screens; powders, suchas talcs, dusting powders, face powders and the like. When used as (an)olfactory component(s) as little as 1% of tricyclic ketone derivative(s)will suffice to impart intense oily, woody amber, leathery, warm spice,earthy camphoraceous, patchouli-like, balsamic, green, cardamom-like,vetiver-like, sweet woody, ambery and minty aromas to variousformulations such as vetiver formulations. Although, generally, no morethan 60% of the tricyclic ketone derivative(s), based on the ultimateend product, is required in the perfume composition, amounts oftricyclic ketone derivative(s) of up to 95% may be used in such perfumecomposition.

When used in perfumed articles such as anionic, cationic and non-ionicdetergents, or dryer-added fabric softener articles, cosmetic powders ordeodorant compositions, from 0.1% up to 5.0% by weight of the tricyclicketone based on the over-all perfumed article weight may be used in theperfumed articles to impart intense oily, woody amber, leathery, warmspice, earthy camphoraceous, patchouli-like, balsam-like, green,cardamom-like, vetiver-like, sweet woody, amber and minty aromas.

In addition, the perfume composition or fragrance composition of ourinvention can contain a vehicle, or carrier for the tricyclic ketonederivative(s). The vehicle can be a liquid such as a non-toxic alcohol,a non-toxic glycol, or the like. The carrier can also be an absorbentsolid, such as a gum (e.g., gum arabic) or components for encapsulatingthe composition (such as gelatin).

An additional aspect of out invention provides an organolepticallyimproved smoking tobacco product and additives therefor, as well asmethods of making the same which overcome problems heretoforeencountered in which specific sweet, floral, woody, spicy, leathery andamber flavor characteristics of natural smoking tobacco (prior to and onsmoking in both the mainstream and the sidestream) as well as coolingeffects, are created, enhanced, modified or augmented and may be readilycontrolled and maintained at the desired uniform level regardless ofvariations in the tobacco components of the blend.

In carrying out this aspect of our invention, we add to smoking tobaccocompositions or a suitable substitute therefor (e.g., dried lettuceleaves), or we add to the wrapper used in producing smoking tobaccoarticles which surround a cylindrical formed body of smoking tobacco, orwe add to the filter which is in intimate contact with both the wrapperand the cylindrical shaped body of tobacco, an aroma and flavor additivecontaining as an active ingredient one or more of the tricyclic ketonesof our invention.

In addition to the tricyclic ketone(s) of our invention other flavoringand aroma additives may be added to the smoking tobacco material orsubstitute therefor either separately or in mixture with the ketone(s)as follows:

I. Synthetic Materials

Beta-ethyl-cinnamaldehyde;

Eugenol;

Dipentene;

Damascenone;

Maltol;

Ethyl maltol;

Delta undecalactone;

Delta decalactone;

Benzaldehyde;

Amyl acetate;

Ethyl butyrate;

Ethyl valerate;

Ethyl acetate;

2-Hexenol-1;

2-Methyl-5-isopropyl-1,3-nonadiene-8-one;

2,6-Dimethyl-2,6-undecadiene-10-one;

2-Methyl-5-isopropylacetophenone;

2-Hydroxy-2,5,5,8a-tetramethyl-1-(2-hydroxyethyl)-decahydronaphthalene;

Dodecahydro-3a,6,6,9a-tetramethylnaphtho-(2,1-b)-furan

4-Hydroxyhexanoic acid, gamma lactone; and

Polyisoprenoid hydrocarbons defined in Example V of U.S. Pat. No.3,589,372 issued on June 29, 1971.

II. Natural Oils

Celery seed oil;

Coffee extract;

Bergamot Oil;

Cocoa extract;

Nutmeg Oil; and

Origanum Oil.

An aroma and flavoring concentrate containing one or more tricyclicketone derivative(s) of our invention and, if desired, one or more ofthe above indicated additional flavoring additives may be added to thesmoking tobacco material, to the filter or to the leaf or paper wrapper.The smoking tobacco material may be shredded, cured, cased and blendedtobacco material or reconstituted tobacco material or tobaccosubstitutes (e.g., lettuce leaves) or mixtures thereof. The proportionsof flavoring additives may be varied in accordance with taste butinsofar as enhancement or the imparting of natural and/or sweet notesand/or cooling notes and/or floral, woody, spicy, leathery or ambernotes, we have found that satisfactory results are obtained if theproportion by weight of the sum total of tricyclic ketone derivative(s)to smoking tobacco material is between 50 ppm and 1,500 ppm(0.015%-0.15%). We have further found that satisfactory results areobtained if the proportion by weight of the sum total of tricyclicketone derivative(s) used to flavoring material is between 1,500 and15,000 ppm (0.15%-1.5%).

Any convenient method for incorporating the tricyclic ketonederivative(s) into the tobacco product may be employed. Thus, thetricyclic ketone derivative(s) taken alone or along with other flavoringadditives may be dissolved in a suitable solvent such as ethanol,diethyl ether and/or volative organic solvents and the resultingsolution may either be spread on the cured, cased and blended tobaccomaterial or the tobacco material may be dipped into such solution. Undercertain circumstances, a solution of the tricyclic ketone derivative(s)taken alone or taken further together with other flavoring additives asset forth above, may be applied by means of a suitable applicator suchas a brush or roller on the paper or leaf wrapper for the smokingproduct, or it may be applied to the filter by either spraying, ordipping, or coating.

Furthermore, it will be apparent that only a portion of the tobacco orsubstitute therefor need be treated and the thus treated tobacco may beblended with other tobaccos before the ultimate tobacco product isformed. In such cases, the tobacco treated may have the tricyclic ketonederivative(s) in excess of the amounts or concentrations above indicatedso that when blended with other tobaccos, the final product will havethe percentage within the indicated range.

In accordance with one specific example of our invention, an aged, curedand shredded domestic burley tobacco is sprayed with a 20% ethyl alcoholsolution ofhexahydro-2,5,5-trimethyl-2H-2,4-a-methanonaphthalene-1(5H)-one havingthe structure: ##STR62## in an amount to provide a tobacco compositioncontaining 800 ppm by weight ofhexahydro-2,5,5-trimethyl-2H-2,4-a-methanonaphthalene-1(5H)-one on a drybasis. Thereafter, the alcohol is removed by evaporation and the tobaccois manufactured into cigarettes by the usual techniques. The cigarettewhen treated as indicated has a desired and pleasant aroma which isdetectable in the main and sidestreams when the cigarette is smoked. Thearoma is described as being sweeter, more aromatic, more tobacco-likeand having sweet, woody, amber notes.

While our invention is particularly useful in the manufacture of smokingtobacco, such as cigarette tobacco, cigar tobacco and pipe tobacco,other tobacco products, formed from sheeted tobacco dust or fines mayalso be used. Likewise, the tricyclic ketone derivative(s) of ourinvention can be incorporated with materials such as filter tipmaterials (e.g., cellulose acetate filters wherein sweet, woody, pineyand/or cooling effects are desired), seam paste, packaging materials andthe like which are used along with tobacco to form a product adapted forsmoking. Furthermore, the tricyclic ketone derivative(s) can be added tocertain tobacco substitutes of natural or synthetic origin (e.g., driedlettuce leaves) and, accordingly, by the term "tobacco" as usedthroughout this specification is meant any composition intended forhuman consumption by smoking or otherwise, whether composed of tobaccoplant parts or substitute materials or both.

It will thus be apparent that the tricyclic ketone(s) of our inventioncan be utilized to alter, modify or enhance sensory properties,particularly organoleptic properties, such as flavor(s) and/orfragrance(s) of a wide variety of consumable materials, such as smokingtobacco, perfumed articles and perfumed compositions in colognes.

The following examples serve to illustrate processes for specificallyproducing the tricyclic ketone(s) of our invention and processes forutilizing said tricyclic ketone(s) for their organoleptic properties.

All parts and percentages given herein are by weight unless otherwisespecified.

EXAMPLES I-IX

The following examples set forth specific embodiments of the reactionscheme: ##STR63## wherein R₁, R₂ and R₃ are each the same or differentand each represents hydrogen or lower alkyl, and one of the dashed linesrepresents a carbon-carbon double bond and each of the other dashedlines represent carbon-carbon single bonds.

The reactions can also be carried out according to the followingreaction scheme: ##STR64##

EXAMPLE I Preparation of a Mixture of1,2,3,4-Tetrahydro-8,8-Dimethyl-2-Tetralincarboxaldehyde andHexahydro-5,5-Dimethyl-2H-2,4-a-Methanonaphthalene-1(5H)-One

Reaction: ##STR65##

1200 grams of Myrac Aldehyde® (trademark of the Givaudan Company ofDelawanna, N.J.) (4-(4-methyl-3-pentenyl)-3-cyclohexenecarboxaldehyde)and is added dropwise with stirring at 45° C. over a 4 hour period to amixture of 600 grams of toluene and 1200 grams of 85% phosphoric acid.At the end of the addition the reaction mass is stirred for anadditional 30 minutes and then poured into 5 l of water. The mass isstirred and the organic layer is further washed twice with 2 liters ofsaturated salt solution. The pH during the second wash is adjusted to pH8 with sodium carbonate. The organic layer is distilled through a shortcolumn to afford 1009 grams of crude product. Fractional redistillationthrough a 11/2"×12" Goodloe packed column affords 911 grams of purifiedproduct (b.p. 94° C., 3 mm). GLC analysis (200° C., isothermal, 10%SE-30 packed column) indicates a composition of 95%8,8-dimethyl-2-tetralincarboxaldehyde and 5%hexahydro-5,5-dimethyl-2H-2,4-a-methanonaphthalene-1(5H)-one.

FIG. 1 shows the nmr spectrum ofhexahydro-5,5-dimethyl-2H-2,4-a-methanonaphthalene-1(5H)-one.

FIG. 2 shows the IR spectrum ofhexahydro-5,5-dimethyl-2H-2,4-a-methanonaphthalene-1(5H)-one.

EXAMPLE II Preparation of a Mixture of1,2,3,4-Tetrahydro-8,8-Dimethyl-2-Tetralincarboxaldehyde andHexahydro-5,5-Dimethyl-2H-2,4-a-Methanonaphthalene-1(5H)-One

Reaction: ##STR66##

A mixture of 31.2 Kg of 85% phosphoric acid and 15.6 Kg of toluene arecharged to a glass lined 50 gallon reactor and heated to 40° C. MyracAldehyde® (31.4 Kg) is added with stirring over a four hour period at40° C. After stirring the mass at 40° C. for 15 minutes, it is pouredwith stirring into a 100 gallon glass lined reactor containing 292 Kg of15% salt solution. The layers are separated with heat and the organicphase is washed with salt water, 5% caustic solution, and salt water,respectively. The toluene is distilled from the organic mass at reducedpressure 50-100 psi. 150 grams of triethylamine, 75 grams of IONOL® (aregistered trademark of the Shell Chemical Company; butylated hydroxytoluene), and 75 grams of PRIMOL® (a registered trademark identifying ahydrocarbon mineral oil produced by Exxon Incorporation of Linden, NewJersey) are added to the mass. Quick distillation through a short columnaffords 22.2 Kg of crude product. Fractional redistillation through a3"×24" Goodloe packed column affords 20.6 Kg of product (b.p. 94° C., 3mm.) GLC analysis (100°-200°, 8°/min., 1/4"×8' 10% Carbowax packedcolumn) indicates 96%1,2,3,4-tetrahydro-8,8-dimethyl-2-tetralincarboxaldehydes and 4%hexahydro-5,5-dimethyl-2H-2,4-a-methanonaphthalene-1(5H)-one.

EXAMPLE III Preparation ofHexahydro-5,5-Dimethyl-2H-2,4-a-Methanonaphthalene-1(5H)-One and aMixture Consisting of1,2,3,4-Tetrahydro-8,8-Dimethyl-2-Tetralincarboxaldehyde andHexahydro-5,5-Dimethyl-2H-2,4-a-Methanonaphthalene-1(5H)-One

Reaction: ##STR67##

A mixture of 30.9 Kg of 85% phosphoric acid and 15.5 Kg of toluene ischarged to a glass lined 50 gallon reactor and heated to 60° C. MyracAldehyde® (30.9 Kg) is added with stirring over a 4 hour period. Thereaction mass is processed as in Example II. Distillation through a3"×24" Goodloe packed column affords 25 Kg of product consisting overallof 75% 1,2,3,4-tetrahydro-8,8-dimethyltetralin and 25% ofhexahydro-5,5-dimethyl-2H-2,4-a-methanonaphthalene-1(5H)-one.Refractionation using a reflux to take off ratio of 9:1 affordsdecahydro-hexahydro-5,5-dimethyl-2H-2,4-a-methanonaphthalene-1(5H)-one.

FIG. 3 represents the GLC trace of the crude reaction mixture, afterremoval of toluene and before distillation (220° C. isothermal, 1/4"×8'10% Carbowax packed column).

EXAMPLE IV Preparation of1,6-Dimethyl-4-(4-Methyl-3-Pentenyl)-3-Cyclohexene-1-Carboxaldehyde

Reaction: ##STR68##

A 3-neck reaction vessel is charged with 100 ml benzene and 50 grams of25% ethyl aluminum dichloride in benzene. A solution containing 320grams myrcene (85% pure), 170 grams 2-methyl-2-butenal, and 200 mlbenzene is fed in at 40°-50° C. over a 1 hour period. The temperature isthen raised to 60° C. and held there for 1/2 hour. An additional 10grams ethyl aluminum dichloride solution mixed with 20 ml benzene isadded and heating is continued for an additional 1/2 hour. The mixtureis then cooled, water is added and the layers are separated. The organiclayer is washed with water and distilled without fractionation to freethe material of residue. Redistillation through an 18" Goodloe packedcolumn provides 199 grams of1,6-dimethyl-4-(4-methyl-3-pentenyl)-3-cyclohexene-1-carboxaldehyde(b.p. 105° C., 0.9 mm).

FIG. 4 represents the nmr spectrum of1,6-dimethyl-4-(4-methyl-3-pentenyl)-3-cyclohexene-1-carboxaldehyde.

FIG. 5 represents the IR spectrum of1,6-dimethyl-4-(4-methyl-3-pentenyl)-3-cyclohexene-1-carboxaldehyde.

EXAMPLE V Preparation of1,2,3,4-Tetrahydro-2,3,8,8-Tetramethyl-2-Tetralincarboxaldehyde

Reaction: ##STR69##

A 1-liter flask equipped with thermometer, mechanical stirrer andaddition funnel is charged with 197 grams of 85% phosphoric acid(Mallinkrodt) and 49 grams toluene. The mixture is stirred at 25°-35° C.as 197 grams of the aldehyde as prepared in Example IV is added over 35minutes. The mixture is then stirred for 5 hours at that temperaturerange at which time complete reaction is indicated by GLC (Carbowaxcolumn). Cooling is applied and 250 ml water is added. The resultingmixture is extracted twice with 500 ml portions of ether. The extractsare washed with 10% sodium hydroxide solution and then with water. Theorganic solution is dried over sodium sulfate and distilled to free theproduct from residue. The resulting oil is then fractionally distilledthrough a 5 ft. Vigreux column to give 92 grams of1,2,3,4-tetrahydro-2,3,8,8-tetramethyl-2-tetralincarboxaldehyde (b.p.113°-115° C., 2 mm).

FIG. 6 represents the nmr spectrum of1,2,3,4-tetrahydro-2,3,8,8-tetramethyl-2-tetralincarboxaldehyde.

FIG. 7 represents the IR spectrum of1,2,3,4-tetrahydro-2,3,8,8-tetramethyl-2-tetralincarboxaldehyde.

FIG. 8 represents the GLC trace of thetetrahydro-2,3,8,8-tetramethyl-2-tetralincarboxaldehyde isomers(100°-220° C., 8°/min., 1/4"×10' 10% Carbowax packed column).

EXAMPLE VI Preparation ofHexahydro-1,2,5,5-Tetramethyl-2H-2,4,-a-Methanonaphthalene-1(5H)-One

Reaction: ##STR70##

A 500 ml reaction flask is charged with 107 grams toluene, 107 grams 85%phosphoric acid, and 107 grams of1,2,3,4-tetrahydro-2,3,8,8-tetramethyl-2-tetralincarboxaldehyde. Themixture is heated at reflux for 1.5 hours at which time 1.0 gramsp-toluenesulfonic acid is added and reflux is continued for anadditional 8.5 hours. The mixture is cooled, diluted with water, and 200ml ether is added. The layers are separated and the organic layer iswashed with water, 10% sodium bicarbonate, and again with water. Afterdrying over magnesium sulfate the solvent is evaporated and theremaining material is distilled without fractionation. The obtaineddistillate is then fractionally distilled through a 5 foot Vigreuxcolumn to give 88 grams of product, b.p. 104°-109° C. (1.0-1.9 mm)consisting of 5% starting material and 95%hexahydro-1,2,5,5-tetramethyl-2H-2,4-a-methanonaphthalene-1(5H)-one.

FIG. 9 represents the nmr spectrum ofhexahydro-1,2,5,5-tetramethyl-2H-2,4-a-methanonaphthalene-1(5H)-one.

FIG. 10 represents the I spectrum ofhexahydro-1,2,5,5-tetramethyl-2H-2,4-a-methanonaphthalene-1(5H)-one.

EXAMPLE VII Preparation ofHexahydro-1,5,5-Trimethyl-2H-2,4-a-Methanonaphthalene-1(5H)-One

Reaction: ##STR71##

1-Methyl-4-(4-methyl-3-penten-1-yl)-3-cyclohexen-1-carboxaldehydecontaining approximately 30%1-methyl-3-(4-methyl-3-penten-1-yl)-3-cyclohexen-1-carboxaldehyde (206grams) is added in 35 minutes with good agitation to a mixture oftoluene (200 ml) and 85% phosphoric acid (150 grams) at 50°-55° C. Themixture is stirred for 27 hours at 75°-85° C. The reaction mass is thenwashed with 1250 grams of 5% salt solution, and the aqueous layer isextracted with 100 mls of toluene. The combined organic phases arewashed successively with 10% sodium carbonate solution and saturatedsalt solution. Distillation affords 37 grams ofhexahydro-1,5,5-trimethyl-2H-2,4-a-methanonaphthalene-1(5H)-one.

FIG. 11 represents the nmr spectrum ofhexahydro-1,5,5-trimethyl-2H-2,4-a-methanonaphthalene-1(5H)-one.

FIG. 12 represents the ¹³ C nmr spectrum ofhexahydro-1,5,5-trimethyl-2H-2,4-a-methanonaphthalene-1(5H)-one.

EXAMPLE VIII Preparation ofHexahydro-2,5,5-Trimethyl-2H-2,4-a-Methanonaphthalene-1(5H)-One

Reaction: ##STR72##

A mixture of 300 ml of toluene and 150 grams of 85% phosphoric acid isstirred at reflux while 618 grams of6-methyl-4-(4-methyl-3-penten-1-yl)-3-cyclohexen-1-carboxaldehyde areadded over a period of 30 minutes. The mixture is stirred for 11 hoursand 117°-118° C. and then some of the toluene is distilled off to raisethe reaction mixture to 135°-137° C. for an additional 2 hours. Themixture is then washed well and fractionally distilled through a11/2"×12" Goodloe packed column to give 160 grams of material which isshown by GLC analysis (220° C., isothermal, 1/4"×10' 10% Carbowax packedcolumn) to be greater than 92%hexahydro-2,5,5-trimethyl-2H-2,4-a-methanonaphthalene-1(5H)-one.

FIG. 13 represents the nmr spectrum ofhexahydro-2,5,5-trimethyl-2H-2,4-a-methanonaphthalene-1(5H)-one.

FIG. 14 represents the IR spectrum ofhexahydro-2,5,5-trimethyl-2-H-2,4-a-methanonaphthalene-1(5H)-one.

EXAMPLE IX Preparation ofHexahydro-1,5,5-Trimethyl-2H-2,4-a-Methanonaphthalene-1(5H)-One

Reaction: ##STR73##

To a solution of1-methyl-4-(4-methyl-3-penten-1-yl)-3-cyclohexene-1-carboxaldehyde (500grams, 2.4 mol) and toluene (500 ml) is added stannic chloride (63grams, 0.24 mol) dropwise at room temperature over a 10 minute period.The mass is heated to gentle reflux for 30 minutes, cooled to roomtemperature and stirred for an additional two hours. When the reactionis complete, the mass is poured into 1000 ml of 5% HCl solution andwashed consecutively with 1000 ml of 5% aqueous sodium carbonate and1000 ml of water. The organic layer is isolated and solvent removedunder reduced pressure. The remaining mass is distilled through a 12"×2"silvered Goodloe column to afford a total of 209 grams of material, ofwhich 73 grams is the desired product (b.p. 93°-94° C., 1.8 mm).

EXAMPLE X Perfume Composition

A perfume composition is prepared by admixing the following ingredientsin the indicated proportions:

    ______________________________________                                        Ingredient              Amount (Grams)                                        ______________________________________                                        n-Decyl Aldehyde        1                                                     n-Dodecyl Aldehyde      2                                                     Methyl Nonyl Acetaldehyde                                                                             0.5                                                   Linalool                50                                                    Linalyl Acetate         70                                                    Phenyl Ethyl Alcohol    100                                                   Petitgrain SA           20                                                    Bergamot Oil            30                                                    Alpha Methyl Ionone     25                                                    Mixture of isomers of 1',2',3',4',                                            5',6',7',8'-octahydro-2',3',8',8'-                                            tetramethyl-2'-acetonaphthones                                                produced by the process of Example II                                         (prior to GLC separation) of U.S.                                             Pat. No. 3,911,018 issued on                                                  October 7, 1975         10                                                    Cyclized Bicyclo C-12 material                                                produced according to the process                                             of Example IV of Canadian Patent                                              854,225 issued October 20, 1970                                                                       5                                                     Iso Bornyl Cyclohexyl Alcohol                                                                         10                                                    Benzyl Acetate          25                                                    2-n-Heptyl Cyclopentanone                                                                             5                                                     Hexahydro-2,5,5-trimethyl-2H-2,4-a-                                           methanonaphthalene-1(5H)-one prepared                                         according to Example VIII                                                                             12.5                                                  TOTAL                   366.0                                                 ______________________________________                                    

The foregoing blend is evaluated and found to have a high degree ofrichness and persistence in its novel amber and patchouli character. Ithas excellent unique leathery notes in addition to earthy notescontributed by the product produced according to Example VIII. This basecomposition can be admixed with aqueous ethanol, chilled and filtered toproduce a finished cologne. The cologne so prepared has an amber aromaleading towards a woody amber, patchouli-like earthy note. The basecomposition can also be used to scent soap or other toilet goods such aslotion, aerosols, sprays and the like.

EXAMPLE XI Vetiver Fragrance

The following mixture is prepared:

    ______________________________________                                        Ingredients             Parts by Weight                                       ______________________________________                                        Hexahydro acetonaphthone derivative                                           prepared according to Example III(B)                                          of U.S. Pat. No. 4,108,799 issued on                                          August 22, 1978         25                                                    Cedrol                  25                                                    Cedrenyl Acetate        5                                                     Isobutyl Quinoline      1                                                     Beta Ionone             2                                                     Caryophyllene           15                                                    Eugenol                 2                                                     Hexahydro-1,5,5-trimethyl-2H-2,4-a-                                           Methanonaphthalene-1(5H)-one prepared                                         according to Example IX 25                                                                            100                                                   ______________________________________                                    

The hexahydro acetonaphthone derivative imparts the rich deep greenwoody note of vetiver to the vetiver fragrance. However, thehexahydro-1,5,5-trimethyl-2H-2,4-a-methanonaphthalene-1(5H)-one ofExample IX imparts a varnishy, woody note of the vetiver family and, inaddition, imparts a green, tart, cardamom=like note so important torounding out this vetiver fragrance and making it more natural-like.

EXAMPLE XII Preparation of a Cosmetic Powder

A cosmetic powder is prepared by mixing in a ball mill, 100 grams oftalcum powder with 0.25 grams of one of the products listed below of ourinvention. The resulting material has an excellent perfume aroma as setforth in the table below:

                  TABLE II                                                        ______________________________________                                        DESCRIPTION        FRAGRANCE                                                  OF COMPOSITION     CHARACTERISTICS                                            ______________________________________                                        A.   Fragrance of Example X                                                                          amber, woody and earthy                                B.   Fragrance of Example XI                                                                         vetiver with intense                                                          varnishy, woody note                                                          and excellent green,                                                          tart, cardamom-like                                                           nuances                                                C.   Hexahydro-5,5-dimethyl-                                                                         sweet, woody, camphor-                                      2H-2,4-a-methanonaph-                                                                           aceous aroma with minty                                     thalene-2(5H)-one and ambery nuances                                     D.   Hexahydro-2,5,5-trimethyl-                                                                      a low-keyed, oily,                                          2H-2,4-a-methanonaphtha-                                                                        woody, amber aroma with                                     lene-1(5H)-one    woody and slightly                                                            leathery undertones.                                                          On purification a deep                                                        woody, earthy camphor-                                                        aceous, patchouli-like                                                        aroma with amber and                                                          leathery undertones.                                   E.   Hexahydro-1,5,5-trimethyl-                                                                      woody aroma with green,                                     2H-2,4-a-methanonaphtha-                                                                        tart, cardamom-like                                         lene-1(5H)-one    undertones.                                            F.   Hexahydro-1,2,5,5-tetra-                                                                        sweet, woody, camphor-                                      methyl-2H-2,4-a-methano-                                                                        aceous, balsamic aroma                                      naphthalene-1(5H)-one                                                                           with patchouli and                                                            deep woody undertones.                                 ______________________________________                                    

EXAMPLE XIII Perfumed Liquid Detergent

Concentrated liquid detergents with aromas as set forth below (whichdetergents are produced from the Lysine salt of n-dodecyl benzenesulfonic acid, as more specifically described in U.S. Pat. No.3,948,818, issued on Apr. 6, 1976) are prepared containing the tricyclicketone derivatives and perfume compositions prepared, supra. They areprepared by adding and homogeneously mixing the appropriate quantity oftricyclic ketone derivative or perfume composition containing same inthe liquid detergent. The detergents all possess excellent aromas as setforth in the table below:

                  TABLE II                                                        ______________________________________                                        DESCRIPTION        FRAGRANCE                                                  OF COMPOSITION     CHARACTERISTICS                                            ______________________________________                                        A.   Fragrance of Example X                                                                          amber, woody and earthy                                B.   Fragrance of Example XI                                                                         vetiver with intense                                                          varnishy, woody note                                                          and excellent green,                                                          tart, cardamom-like                                                           nuances                                                C.   Hexahydro-5,5-dimethyl-                                                                         sweet, woody, camphor-                                      2H-2,4-a-methanonaph-                                                                           aceous aroma with minty                                     thalene-2(5H)-one and ambery nuances                                     D.   Hexahydro-2,5,5-trimethyl-                                                                      a low-keyed, oily,                                          2H-2,4-a-methanonaphtha-                                                                        woody, amber aroma with                                     lene-1(5H)-one    woody and slightly                                                            leathery undertones.                                                          On purification a deep                                                        woody, earthy camphor-                                                        aceous, patchouli-like                                                        aroma with amber and                                                          leathery undertones.                                   E.   Hexahydro-1,5,5-trimethyl-                                                                      woody aroma with green,                                     2H-2,4-a-methanonaphtha-                                                                        tart, cardamom-like                                         lene-1(5H)-one    undertones.                                            F.   Hexahydro-1,2,5,5-tetra-                                                                        sweet, woody, camphor-                                      methyl-2H-2,4-a-methano-                                                                        aceous, balsamic aroma                                      naphthalene-1(5H)-one                                                                           with patchouli and                                                            deep woody undertones.                                 ______________________________________                                    

EXAMPLE XIV Preparation of a Cologne and Handkerchief Perfume

Perfume compositions and tricyclic ketone derivatives prepared, supra,as indicated in the table below are incorporated into colognes atconcentrations of 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, and 5.0% in 80%,85%, 90% and 95% aqueous food grade ethanol; and into handkerchiefperfumes at concentrations of 10%, 15%, 20%, 30%, 40% and 50% (in 90%,and 95% aqueous food grade ethanol). Distinct and definitive fragrancearomas as set forth in the table below are imparted to the colognes andto the handkerchief perfumes:

                  TABLE II                                                        ______________________________________                                        DESCRIPTION        FRAGRANCE                                                  OF COMPOSITION     CHARACTERISTICS                                            ______________________________________                                        A.   Fragrance of Example X                                                                          amber, woody and earthy                                B.   Fragrance of Example XI                                                                         vetiver with intense                                                          varnishy, woody note                                                          and excellent green,                                                          tart, cardamom-like                                                           nuances                                                C.   Hexahydro-5,5-dimethyl-                                                                         sweet, woody, camphor-                                      2H-2,4-a-methanonaph-                                                                           aceous aroma with minty                                     thalene-2(5H)-one and ambery nuances                                     D.   Hexahydro-2,5,5-trimethyl-                                                                      a low-keyed, oily,                                          2H-2,4-a-methanonaphtha-                                                                        woody, amber aroma with                                     lene-1(5H)-one    woody and slightly                                                            leathery undertones.                                                          On purification a deep                                                        woody, earthy camphor-                                                        aceous, patchouli-like                                                        aroma with amber and                                                          leathery undertones.                                   E.   Hexahydro-1,5,5-trimethyl-                                                                      woody aroma with green,                                     2H-2,4-a-methanonaphtha-                                                                        tart, cardamom-like                                         lene-1(5H)-one    undertones.                                            F.   Hexahydro-1,2,5,5-tetra-                                                                        sweet, woody, camphor-                                      methyl-2H-2,4-a-methano-                                                                        aceous, balsamic aroma                                      naphthalene-1(5H)-one                                                                           with patchouli and                                                            deep woody undertones.                                 ______________________________________                                    

EXAMPLE XV Preparation of Soap Composition

One hundred grams of soap chips (obtained from Ivory® Soap) (a trademarkof Proctor & Gamble Company of Cincinnati, Ohio) are mixed with twograms of the materials as set forth in the table below until asubstantially homogeneous composition is obtained. The resultingcomposition is melted at 180° C. for a period of 4 hours under 8atmospheres nitrogen pressure. The resulting melt is cooled and formedinto a soap bar. Each of the soap bars has an aroma set forth in thetable below:

                  TABLE II                                                        ______________________________________                                        DESCRIPTION        FRAGRANCE                                                  OF COMPOSITION     CHARACTERISTICS                                            ______________________________________                                        A.   Fragrance of Example X                                                                          amber, woody and earthy                                B.   Fragrance of Example XI                                                                         vetiver with intense                                                          varnishy, woody note                                                          and excellent green,                                                          tart, cardamom-like                                                           nuances                                                C.   Hexahydro-5,5-dimethyl-                                                                         sweet, woody, camphor-                                      2H-2,4-a-methanonaph-                                                                           aceous aroma with minty                                     thalene-2(5H)-one and ambery nuances                                     D.   Hexahydro-2,5,5-trimethyl-                                                                      a low-keyed, oily,                                          2H-2,4-a-methanonaphtha-                                                                        woody, amber aroma with                                     lene-1(5H)-one    woody and slightly                                                            leathery undertones.                                                          On purification a deep                                                        woody, earthy camphor-                                                        aceous, patchouli-like                                                        aroma with amber and                                                          leathery undertones.                                   E.   Hexahydro-1,5,5-trimethyl-                                                                      woody aroma with green,                                     2H-2,4-a-methanonaphtha-                                                                        tart, cardamom-like                                         lene-1(5H)-one    undertones.                                            F.   Hexahydro-1,2,5,5-tetra-                                                                        sweet, woody, camphor-                                      methyl-2H-2,4-a-methano-                                                                        aceous, balsamic aroma                                      naphthalene-1(5H)-one                                                                           with patchouli and                                                            deep woody undertones.                                 ______________________________________                                    

EXAMPLE XVI Preparation of Liquid Detergent

Concentrated liquid detergents with aromas as set forth below containing0.2%, 0.5% and 1.2% of the compositions as set forth in the table beloware prepared by adding the appropriate quantity of the indicatedcomposition as set forth below to liquid detergent known as P-87. Thearomas of the liquid detergent increase with increasing concentration ofcomposition as set forth in the table below:

                  TABLE II                                                        ______________________________________                                        DESCRIPTION        FRAGRANCE                                                  OF COMPOSITION     CHARACTERISTICS                                            ______________________________________                                        A.   Fragrance of Example X                                                                          amber, woody and earthy                                B.   Fragrance of Example XI                                                                         vetiver with intense                                                          varnishy, woody note                                                          and excellent green,                                                          tart, cardamom-like                                                           nuances                                                C.   Hexahydro-5,5-dimethyl-                                                                         sweet, woody, camphor-                                      2H-2,4-a-methanonaph-                                                                           aceous aroma with minty                                     thalene-2(5H)-one and ambery nuances                                     D.   Hexahydro-2,5,5-trimethyl-                                                                      a low-keyed, oily,                                          2H-2,4-a-methanonaphtha-                                                                        woody, amber aroma with                                     lene-1(5H)-one    woody and slightly                                                            leathery undertones.                                                          On purification a deep                                                        woody, earthy camphor-                                                        aceous, patchouli-like                                                        aroma with amber and                                                          leathery undertones.                                   E.   Hexahydro-1,5,5-trimethyl-                                                                      woody aroma with green,                                     2H-2,4-a-methanonaphtha-                                                                        tart, cardamom-like                                         lene-1(5H)-one    undertones.                                            F.   Hexahydro-1,2,5,5-tetra-                                                                        sweet, woody, camphor-                                      methyl-2H-2,4-a-methano-                                                                        aceous, balsamic aroma                                      naphthalene-1(5H)-one                                                                           with patchouli and                                                            deep woody undertones.                                 ______________________________________                                    

EXAMPLE XVII

A tobacco blend is prepared as follows:

    ______________________________________                                        Ingredient          Parts by Weight                                           ______________________________________                                        Bright              40.1                                                      Burley              24.9                                                      Maryland            1.1                                                       Turkish             11.6                                                      Stem (flue-cured)   14.2                                                      Glycerine           2.8                                                       Water               5.3                                                       ______________________________________                                    

The following flavor formulation is prepared:

    ______________________________________                                        Ingredient           Parts by Weight                                          ______________________________________                                        Ethyl Butyrate       0.05                                                     Ethyl Valerate       0.05                                                     Maltol               2.00                                                     Cocoa Extract        26.00                                                    Coffee Extract       10.00                                                    95% Ethanol (aqueous)                                                                              20.00                                                    Water                41.90                                                    ______________________________________                                    

The above-mentioned tobacco blend is divided into four portions: PortionA; Portion B; Portion C; and Portion D. Portion C and D are eachcombined separately with the above-mentioned tobacco flavor formulation,at the rate of 0.2%. Each of Portions A, B, C and D are thenmanufactured into cigarettes. The cigarettes containing tobacco PortionsA and C are left as is. To the cigarettes manufactured from tobaccoPortions B and D is added at the rates of 200 and 2000 ppmhexahydro-2,5,5-trimethyl-2H-2,4-a-methanonaphthalene-1(5H)-one preparedaccording to Example VIII. The cigarettes are then evaluated by pairedcomparison and the results are as follows.

The aroma on smoking of cigarettes produced from tobacco Portions B andD is found to be more sweet, floral, woody, spicy and leathery-like withenhanced tobacco taste and tobacco aroma, than the aroma of thosecigarettes produced from Portions A and C.

In smoke flavor (main stream) the cigarettes produced from Portion D arefound to be more aromatic and sweeter with a cooling effect.

In smoke flavor (side stream or room aroma) the cigarettes produced fromPortion D are found to be sweet, aromatic, more woody and more spicy,i.e., having an oriental, balsamic character.

Thus, the product produced according to Example VIII modifies the sidestream and the main stream smoke aromas at making it more pleasant andmore natural tobacco-like.

All cigarettes are evaluated for smoke flavor with a 20 mm celluloseacetate filter.

EXAMPLE XVIII

Utilizing the procedure of Example I of Column 15 of U.S. Pat. No.3,632,396, a nonwoven cloth substrate useful as a dryer-added fabricsoftening article of manufacture is prepared wherein the substrate, thesubstrate coating and the outer coating and the perfuming material areas follows:

1. a water "dissolvable" paper ("Dissolvo Paper"):

2. Adogen 448 (m.p. about 140° F.) as the substrate coating; and

3. an outer coating having the following formulation (m.p. about 150°F.):

57 percent C₂₀₋₂₂ HAPS

22 percent isopropyl alcohol

20 percent antistatic agent

1 percent of a composition as set forth in the table below having thearoma properties as set forth in the table below:

                  TABLE II                                                        ______________________________________                                        DESCRIPTION        FRAGRANCE                                                  OF COMPOSITION     CHARACTERISTICS                                            ______________________________________                                        A.   Fragrance of Example X                                                                          amber, woody and earthy                                B.   Fragrance of Example XI                                                                         vetiver with intense                                                          varnishy, woody note                                                          and excellent green,                                                          tart, cardamom-like                                                           nuances                                                C.   Hexahydro-5,5-dimethyl-                                                                         sweet, woody, camphor-                                      2H-2,4-a-methanonaph-                                                                           aceous aroma with minty                                     thalene-2(5H)-one and ambery nuances                                     D.   Hexahydro-2,5,5-trimethyl-                                                                      a low-keyed, oily,                                          2H-2,4-a-methanonaphtha-                                                                        woody, amber aroma with                                     lene-1(5H)-one    woody and slightly                                                            leathery undertones.                                                          On purification a deep                                                        woody, earthy camphor-                                                        aceous, patchouli-like                                                        aroma with amber and                                                          leathery undertones.                                   E.   Hexahydro-1,5,5-trimethyl-                                                                      woody aroma with green,                                     2H-2,4-a-methanonaphtha-                                                                        tart, cardamom-like                                         lene-1(5H)-one    undertones.                                            F.   Hexahydro-1,2,5,5-tetra-                                                                        sweet, woody, camphor-                                      methyl-2H-2,4-a-methano-                                                                        aceous, balsamic aroma                                      naphthalene-1(5H)-one                                                                           with patchouli and                                                            deep woody undertones.                                 ______________________________________                                    

Fabric-softening compositions prepared as set forth above having theabove aroma characteristics essentially consist of a substrate having aweight of about 3 grams per 100 square inches, a substrate coating ofabout 1.85 grams per 100 square inches of substrate and an outer coatingof about 1.4 grams per 100 square inches of substrate, thereby providinga total aromatized substrate and outer coating weight ratio of about 1:1by weight of the substrate. The aromas as set forth in Table II aboveare imparted in a pleasant manner to the head space in the dryer onoperation thereof using the said dryer added fabric softening nonwovenfabric.

EXAMPLE XIX

Granular detergent compositions prepared according to United KingdomPatent Specification No. 1,501,498 having the following formulae areprepared by spray-drying the following mixtures as indicated in thecolumns headed XIX A, XIX B, XIX C and XIX D:

    ______________________________________                                                   COMPOSITION IN % BY WEIGHT                                                      Example  Example  Example                                                                              Example                                 Ingredient   XIX A    XIX B    XIX C  XIX D                                   ______________________________________                                        Sodium salt of                                                                             14.1     14.1     14.1   14.1                                    ethoxylated fatty                                                             alcohol sulfate                                                               having an average                                                             of about 2.25 moles                                                           of ethylene oxide                                                             per mole of fatty                                                             alcohol (1)                                                                   Sodium tallow alkyl                                                                        2.4      2.4      2.4    2.4                                     sulfate                                                                       Sodium silicate                                                                            0.0      2.0      6.0    0.0                                     solids ratio:                                                                 SiO.sub.2 /Na.sub.2 O = 2.0                                                   Sodium silicate                                                                            1.0      0.0      0.0    6.0                                     solids ratio:                                                                 SiO.sub.2 /Na.sub.2 O = 3.2                                                   Sodium tripolyphos-                                                                        24.0     24.0     24.0   24.0                                    phate                                                                         Na.sub.12 (AlO.sub.2 . SiO.sub.2).sub.12 .                                                 18.0     18.0     18.0   18.0                                    27H.sub.2 O (2)                                                               Moisture     10.0     10.1     9.9    10.2                                    Sodium sulfate                                                                             25.0     25.0     20.0   20.0                                    Minor ingredients                                                                          4.0      2.4      3.6    2.3                                     including sodium                                                              toluene sulfonate,                                                            trisodium sulfo-                                                              succinate, dyes,                                                              brighteners                                                                   hexahydro-5,5-dimeth-                                                                      1.5      0.0      0.0    0.0                                     yl-2H-2,4-a-methano-                                                          naphthalene-1(5H)-one                                                         hexahydro-2,5,5-tri-                                                                       0.0      2.0      0.0    0.0                                     methyl-2H-2,4-a-meth-                                                         anonaphthalene-1(5H)-                                                         one                                                                           hexahydro-1,5,5-tri-                                                                       0.0      0.0      2.0    0.0                                     methyl-2H-2,4-a-meth-                                                         anonaphthalene-1(5H)-                                                         one                                                                           hexahydro-1,2,5,5-                                                                         0.0      0.0      0.0    3.0                                     tetramethyl-2H-2,4-a-                                                         methanonaphthalene-                                                           1(5H)-one                                                                     ______________________________________                                         (1) Fatty alcohol composition: 66%C.sub.14 ; 33%C.sub.16 ;                     (2) Prepared as described in United Kingdom Patent 1,501,498; average        particle size diameter 2 microns.                                        

Laundry solutions containing the above detergent compositions are usedto launder fabrics. Each of the laundry compositions both prior to andon laundering gives rise to the following aromas:

    ______________________________________                                        NAME OF COMPOUND    FRAGRANCE                                                 ______________________________________                                        hexahydro-5,5-dimethyl-2H-                                                                        sweet, woody, camphor-                                    2,4-a-methanonaphthalene-                                                                         aceous aroma with minty                                   1(5H)-one           and ambery nuances                                        hexahydro-2,5,5-trimethyl-                                                                        low-keyed, oily, woody,                                   2H-2,4-a-methanonaphthalene                                                                       amber aroma with woody                                    1(5H)-one           and slightly leathery                                                         undertones. On purifi-                                                        cation a deep woody,                                                          earthy camphoraceous,                                                         patchouli-like aroma                                                          with amber and leathery                                                       undertones                                                hexahydro-1,5,5-trimethyl-                                                                        woody aroma with green,                                   2H-2,4-a-methanonaphthalene-                                                                      tart, cardamom-like un-                                   1(5H)-one           dertones                                                  hexahydro-1,2,5,5-tetramethyl-                                                                    sweet, woody, camphor-                                    2H-2,4-a-methanonaphthalene-                                                                      aceous, balsamic aroma                                    1(5H)-one           with patchouli and deep                                                       woody undertones                                          ______________________________________                                    

EXAMPLE XX Perfumed Liquid Detergent

Concentrated liquid detergents having aromas as set forth in the tablebelow are prepared containing 0.10%, 0.15%, 0.20%, 0.40% and 0.80% andone of the materials as set forth in the table below. They are preparedby adding and homogeneously mixing the appropriate quantity of mixtureof perfume materials in liquid detergent. The liquid detergent is abuilder-free liquid detergent consisting of (a) 50% of a non-ionicsurfactant having an HLB of 8.0 and a critical micelle concentration of0.007, weight percent at 25° C.; (b) an ionic surfactant which istriethanolamine citrate; and (c) one weight percent of diethanolamineprepared according to United Kingdom Patent Specification No. 1,491,603.

The detergents all possess fragrances as set forth in the table below,the intensity increasing with greater concentrations of fragrancematerial:

                  TABLE II                                                        ______________________________________                                        DESCRIPTION        FRAGRANCE                                                  OF COMPOSITION     CHARACTERISTICS                                            ______________________________________                                        A.   Fragrance of Example X                                                                          amber, woody and earthy                                B.   Fragrance of Example XI                                                                         vetiver with intense                                                          varnishy, woody note                                                          and excellent green,                                                          tart, cardamom-like                                                           nuances                                                C.   Hexahydro-5,5-dimethyl-                                                                         sweet, woody, camphor-                                      2H-2,4-a-methanonaph-                                                                           aceous aroma with minty                                     thalene-2(5H)-one and ambery nuances                                     D.   Hexahydro-2,5,5-trimethyl-                                                                      a low-keyed, oily,                                          2H-2,4-a-methanonaphtha-                                                                        woody, amber aroma with                                     lene-1(5H)-one    woody and slightly                                                            leathery undertones.                                                          On purification a deep                                                        woody, earthy camphor-                                                        aceous, patchouli-like                                                        aroma with amber and                                                          leathery undertones.                                   E.   Hexahydro-1,5,5-trimethyl-                                                                      woody aroma with green,                                     2H-2,4-a-methanonaphtha-                                                                        tart, cardamom-like                                         lene-1(5H)-one    undertones.                                            F.   Hexahydro-1,2,5,5-tetra-                                                                        sweet, woody, camphor-                                      methyl-2H-2,4-a-methano-                                                                        aceous, balsamic aroma                                      naphthalene-1(5H)-one                                                                           with patchouli and                                                            deep woody undertones.                                 ______________________________________                                    

What is claimed is:
 1. A process for augmenting or enhancing the aromaof a dryer-added fabric softening article comprising the step ofintimately admixing with the coating composition for the outer coatingof said dryer-added fabric softening article from 0.1% up to 5.0% byweight based on said fabric softener article of at least onesubstantially pure tricyclic ketone having the structure: ##STR74##wherein R₁, R₂ and R₃ are the same or different and each representshydrogen or methyl.